Methods of combatting fungi,nematodes and insects with sulfinyl thiol-and dithio-phosphates

ABSTRACT

SULFINYL THIO- AND DITHIO-PHOSPHATES, I.E., O,O-DIALKYLS-(TRICHLOROETHYL AND DICHOROVINYL SULFINYL)-THIOL- AND DITHIO-PHOSPHATES, OR O,O-DIALKYL-S-(TRICHLOROETHYL THIONYL AND DICHLOROVINYL THIONYL) THIOL- AND THIONOTHIOL-PHOSPHATES, WHICH POSSESS STRONG FUNGICIDAL, NEMATOCIDAL AND INSECTICIDAL PROPERTIES AND WHICH MAY BE PRODUCED BY CONVENTIONAL METHODS.

United States Patent METHODS OF COMBATTIN G FUNGI, NEMATODES AND INSECTS WITH SULFINYL THIOL- AND DITHIO-PHOSPHATES Paul C. Aichenegg, Prairie Village, Kans., and Richard A. Thornhill, Kansas City, Mo., assignors to Baychem Corporation, New York, N.Y.

No Drawing. Original application Mar. 4, 1969, Ser. No. 804,272, now Patent No. 3,629,375. Divided and this application Mar. 1, 1971, Ser. No. 119,853

Int. Cl. A01n 9/ 36 US. Cl. 424-208 12 Claims ABSTRACT OF THE DISCLOSURE Sulfinyl thioand dithio-phosphates, i.e., 0,0-dialkyl- S-(trichloroethyl and dichlorovinyl sulfinyl)-thioland dithio-phosphates, or 0,0-dialkyl-S-(trichloroethyl thionyl and dichlorovinyl thionyl) thioland thionothiol-phosphates, which possess strong fungicidal, nematocidal and insecticidal properties and which may be produced by conventional methods.

This application is a division of application Ser. No. 804,272, filed Mar. 4, 1969, now US. Pat. No. 3,629,375.

The present invention relates to and has for its objects the provision of particular new sulfinyl thioland dithiophosphates, i.e. 0,0-dialkyl-S-(trichloroethyl and dichlorovinyl sulfinyl)-thioland dithio-phosphates, or 0,0- dialkyl-S-(trichloroethyl thionyl and dichlorovinyl thionyl) thioland thionothiol-phosphates, which possess valuable pesticidal, especially fungicidal, nematocidal and insecticidal, properties, active compositions in the form of mixtures of such compounds with solid and liquid dispersible carrier vehicles, and methods for producing such compounds and for using such compounds in a new way, especially for combating fungal diseases, nematode infestations, and insect pests and the like, with other and further objects becoming apparent from a study of the within specification and accompanying examples.

It is not believed that any sulfinyl thioland/or dithiophosphates of analogous constitution are known and/or are known to possess combined fungicidal, nematocidal and insecticidal properties.

It has now been found, in accordance with the present invention, that the particular new sulfinyl thioland dithio-phosphates of the general formula in which R is alkyl of l4 carbon atoms,

R is trichloroethyl or dichlorovinyl, especially having at most one a-chloro group, and

X is oxygen or sulfur,

exhibit strong fungicidal, nematocidal and insecticidal properties.

It has been furthermore found, in accordance with the present invention, that'the compounds of Formula I above may be produced by a process which comprises:

(a) Reacting a thiolor dithio-phosphoric acid ester of the formula in which R and X are the same as defined above, with 3,708,582 Patented Jan. 2, 1973 trichloroethyl or dichlorovinyl sulfinyl chloride of the respective formulae 3'! i n) in which R, X and Y are the same as defined above, with a dehydrochlorinating agent in the presence of a solvent.

Surprisingly, the sulfinyl thioland dithio-phosphates of the instant invention are chemically completely novel compounds unobvious over the prior art. Because of their combined fungicidal, nematocidal and insecticidal properties and their broad spectrum of activity, the instant compounds therefore represent a valuable enrichment of the art.

According to reaction variant (a), if for instance 2,2- dichlorovinyl sulfinyl chloride (IVa) and 0,0-dimethyl dithiophosphoric acid (Ila) are used as starting materials, the course of the reaction can be represented by the following equation:

According to reaction variant (b), the corresponding vinyl sulfinyl thioland dithio-phosphates of Formula I, i.e. in which R is vinyl, may alternatively be obtained by dehydrochlorinating the trichloroethyl sulfinyl thiolor dithio-phosphate of Formula Ii in the presence of a dehydrochlorinating agent such as tertiary amine or an alkoxide, according to the following equation:

(Iib) Advantageously, in accordance with the present invention, in the various formulae herein,

R represents:

Lower alkyl hydrocarbon of 1-4 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec.-butyl, tert.-butyl, and the like, especially 0 or C alkyl, and more especially methyl and ethyl;

R' represents:

Trichloroethyl, preferably having at least one terminal or ,B-chloro group, i.e. at most one chloro group in aposition to the adjacent sulfinyl group, such as 2,2,2- and 1,2,2-trichloro ethyl; or

Dichlorovinyl, i.e. having at least one terminal or B- chloro group, i.e. at most one chloro group in DL-pOSltlOn to the adjacent sulfinyl group, such as 2,2- and 1,2-di chlorovinyl; and

X represents: oxygen; or sulfur.

Preferably, R is C alkyl, R is trichloroethyl or dichlorovinyl and X is oxygen or sulfur, both symbols R being the same.

Furthermore, especially where R is C alkyl, R is preferably 2,2,2-trichloroethyl when X is oxygen or sulfur; or R is preferably 1,2,2-trichloroethy1 when X is oxygen or sulfur, or R is preferably 2,2-dichlorovinyl when X is oxygen or sulfur; or R is preferably 1,2-dichlorovinyl when X is oxygen or sulfur.

Preferred compounds include:

(9) 0,0-dimethyl-S- (2,Z-dichlorovinyl-sulfinyl)-thiolphosphate;

( 14) 0,0-dimethyl-S-( 1,2,2-trichloroethyl-sulfinyl dithiophosphate;

(8) 0,0-dimethyl-S-( 1,Z-dichlorovinyl-sulfinyl thiolphosphate;

( 10) 0,0-diethyl-S-( l,2,2-trichloroethyl-sulfinyl dithiophosphate;

(3 0,0-diethyl-S- (2,2,Z-trichloroethyl-sulfinyl) thiolphosphate;

(4) 0,0-diethyl-S-( 1,Z-dichlorovinyl-sulfinyl thiolphosphate;

(1 l) 0,0-diethyl-S-(2,2,2-trichloroethyl-sulfinyl)-dithiophosphate; and

(16) 0,0-dimethyl-S-(1,2-dichlorovinyl-sulfinyl)- dithiophosphate.

The types of thioland dithio-phosphoric acid esters usable as starting materials in accordance with process variant (a) of the present invention are clearly characterized by Formula 11 noted above.

These 0,0-dialkyl-thioland dithio-phosphoric acid esters are well known and can be prepared on an industrial scale.

As examples of such thioland dithio-phosphoric acid esters which can be used as starting materials for process variant (a) according to the present invention, there may be mentioned in particular:

0,0-dimethyl-thiol-phosphoric acid, 0,0-dimethyl-dithio-phosphoric acid, 0,0-diethyl-dithio-phosphoric acid, 0,0-diethyl-thiol-phosphoric acid, 0,0-diisopropyl-dithio-phosphoric acid, 0,0-di-n-butyl-thiol-phosphoric acid, 0,0-di-sec.-butyl-dithio-phosphoric acid, and the like.

The types of trichloroethyl and dichlorovinyl sulfinyl chlorides usable as starting materials in accordance with process variant (a) of the present invention are clearly characterized by Formulae III and IV noted above.

The sulfinyl chlorides may be prepared by reacting the corresponding sulfenyl chloride in acetic acid with an excess of chlorine at a temperature not exceeding 7 C. during the chlorine addition. The reaction mixture is then allowed to warm up to room temperature and to stand overnight. The mixture is then heated'to 65-75 C. for one hour, volatiles are stripped off and the product fractionated in high vacuum.

Another mode of preparation of these starting sulfinyl chlorides that can be used with advantage for process variant (a) is that as described by I. Douglass, J.O.C. 33, 2105, 1968, which requires the use of the corresponding disulfides as starting materials in place of the sulfenyl chlorides.

The starting trichloroethyl and dichlorovinyl sulfenyl chlorides usable for process variant (a) may also be prepared from the corresponding disulfides as described in US. Pat. No. 3,293,304.

As examples of such sulfinyl chlorides which can be used as starting materials for process variant (a) according to the present invention there may be mentioned in particular:

1,2,2-trichloroethyl sulfinyl chloride, 2,2,2-trichloroethyl sulfinyl chloride, 1,2-dichlorovinyl sulfinyl chloride, and 2,2-dichlorovinyl sulfinyl chloride.

In addition to the reagents employed, the reaction according to process variant (a) may be carried out optionally in the presence of an inert organic solvent (this term also includes a mere diluent). Examples of such solvents include hydrocarbons such as petroleum ether, hexane, benzene, toluene and chlorinated hydrocarbons such as methylene chloride, dichloroethane, chloroform, carbon tetrachloride, chlorobenzene, dichlorobenzene, and the like; but the preferred solvents are chloroform or carbon tetrachloride. Other solvents such as ethers (tetrahydrofuran, diethyl ether, dioxane), esters (ethyl acetate) or ketones (acetone, cyclohexanone), and the like, have been found to result in decreased yields of the subject compounds but are still usable despite this disadvantage.

The reaction temperature for process variant (a) can be varied within a fairly wide range. In general, the reaction is carried out at substantially between about 20- 150 C., peferably between about 50-100 C.

In general, for process variant (a), the reactants are used in approximately equimolar proportions or an excess of the thiol or dithio phosphoric acid ester of Formula II may be used with advantage. The latter can be removed by washing the obtained crude reaction mixture with water. The reaction can for example be carried out in such a manner that the sulfinyl chloride of Formula III or IV is added dropwise to a solution or suspension of the thiol or dithio phosphoric acid ester at room temperature (25 C.) allowing the temperature to rise (exothermic reaction), and keeping the reaction mixture at between 50 and C. until the evolution of hydrogen chloride has ended.

Furthermore, in connection with the final work-up according to the process variant (a), washing with water, drying of the organic solution over M gSO, and evaporating the solvent yields the corresponding sulfinyl thiopho-sphate of Formula I in pure form.

For purocess variant (b) the preferred dehydrochlorin-at ing agent used is triethylamine in an inert organic solvent such as petroleum ether, but alkali, i.e. alkali metal alkanolate such as sodium ethoxide in ethyl alcohol or the like, as solvent, can also be used successfully.

In general, for process variant (b), an equimolar amount of the dehydrochlorinating agent, i.e. base, is added to the trichloroethyl sulfinyl thiolor dithiophosphate at between 25 and 50 C. and the reaction mixture held at temperatures ranging from 50-l00 C. until the formation of the base hydrochloride, e.g. amine hydrochloride or sodium chloride, respectively, has ended.

For the final work-up according to process variant (b), filtration, washing with water, drying of the organic solution over MgSO and high vacuum evaporation of the solvent used yields the corresponding vinyl sulfinyl phosphate in pure form.

Advantageously, the active compounds according to the present invention exhibit strong fungicidal, nematocidal and insecticidal properties with comparatively low toxicity to warm-blooded creatures and concomitantly low phytotoxicity. Hence, the instant compounds are suitable for use as plant protection agents, and in the hygiene field, for the control of fungi, nematodes and insects.

As to the fungicidal properties, the instant compounds possess a broad spectrum of activity.

Thus, the instant compounds can be used for the control of fungi from the most widely different classes of fungi, such as for example Archimycetes, Phycomycetes, Ascomycetes, Basidiomycetes, Fungi Imperfecti, and the like. The instant compounds can give particularly effective results against parasitic fungi on above-ground parts of plants, fungi causing tracheornycosis, which attack the plant from the soil, seed-borne fungi, and soil-borne fungi, such as the organisms Ceratocystis ulmi, Colletotricum obiculare, Fusarium lycopersici, Fusarium nivale, Helminthosporium satirum, Rhizoctonia solani, Vertzcz'llium albaatrum, Pythium, Alternaria, Ustilago, and the like.

As to the nematocidal properties, the instant compounds have outstanding activity. Thus, the instant compounds can also be used for the control of nematodes of the saprophytic type Panagrellus and Rhabditis ssp.; and the like.

As to the insecticidal properties, the insecticidal action sets in rapidly and is long-lasting.

Thus, the instant compounds can furthermore be used with very favorable results for the control of noxious biting insects and Diptera.

With the biting insects contemplated herein there are classed, in the main, beetles, such as the confused flour beetle (Tribolium confusum).

The Diptera contemplated herein comprise in particular flies, such as the housefly (Musca domestica).

The active compounds according to the instant invention can be utilized, if desired, in the :form of the usual formulations or compositions with conventional inert pesticidal diluents or extenders, i.e. conventional pesticidal dispersible carrier vehicles, such as solutions, emulsions, suspensions, emulsifiable concentrates, spray powders, pastes, soluble powders, dusting agents, granules, etc. These are prepared in known manner, for instance by extending the active compounds with conventional pesticidal dispersible liquid diluent carriers and/or dispersible solid carriers optionally with the use of carrier vehicle assistants, e.g. conventional pesticidal surfaceactive agents, including emulsifying agents and/or dispersing agents, whereby, for example, in the case Where water is used as diluent, organic solvents may be added as auxiliary solvents. The following may be chiefly considered for use as conventional carrier vehicles for this purpose: Inert dispersible liquid diluent carriers including inert organic solvents, such as aromatic hydrocarbons (e.g. benzene, toluene, xylene, etc.), ha ogenated, especially chlorinated, aromatic hydrocarbons (e.g. chlorobenzenes, etc.), paraffins (e.g. petroleum fractions), chlorinated aliphatic hydrocarbons (e.g. methylene chloride, etc., alcohols (e.g. methanol, ethanol, propanol, butanol, etc.), amines (e.g. ethanolamine, etc.), ethers, etheralcohols (e.g. glycol monomethyl ether, etc.), amides (e.g. dimethyl formamide, etc.), sulfoxides (e.g. dimethyl sufoxide, etc.), ketones (e.g. acetone, etc.), and/or water; as well as inert dispersible finely divided solid carriers, such as ground natural mineral (e.g. kaolins, alumina, silica, chalk, i.e. calcium carbonate, talc, kieselguhr, etc.) and ground synthetic minerals (e.g. highly dispersed silicic acid, silicates (e.g. alkali lsilicates, etc.); whereas the following may be chiefly considered for use as conventional carrier vehicle assistants, e.g. surface-active agents, for this purpose: emulsifying agents, such as non-ionic and/ or anionic emulsifying agents (e.g. polyethylene oxide esters of fatty acids, polyethylene oxide ethers of fatty alcohols, alkyl sulfonates, aryl sulfonates, etc., and especially alkyl arylpolyglycol ethers, magnesium stearate, sodium oleate, etc.) and/or dispersing agents, such as lignin, sulfite waste liquors, methyl cellulose, etc.

Such active compounds may be employed alone or in the form of mixtures with one another and/or with such solid and/ or liquid dispersible carrier vehicles and/ or with other known compatible active agents, especially plant protection agents, such as other fungicides, insecticides or nematocides, or herbicides, bactericides, etc., if desired, or in the form of particular dosage preparations for specific application made therefrom, such as solutions, emulsions, suspensions, powders, pastes, and granules which are thus ready for use.

As concerns commercially marketed preparations, these generally contemplate carrier composition mixtures in which the active compound is present in an amount substantially between about 0.1-95 and preferably 05-90%, by weight of the mixture, whereas carrier composition mixtures suitable for direct application or field application generally contemplate those in which the active compound is present in an amount substantially between about 0.000l-2.0%, preferably OBI-0.8%, by Weight of the mixture. Thus, the present invention contemplates overall compositions which comprise mixtures of a conventional dispersible carrier vehicle such as (l) a dispersible inert finely divided carrier solid and/ or (2) a dispersible carrier liquid such as an inert organic solvent and/or water preferably including a surface-active effective amount of a carriervehicle assistant, e.g. surface-active agent, such as an emulsifying agent and/ or a dispersing agent, and an amount of the active compound which is effective for the purpose in question and which is generally between about 0.000l%, and preferably 0.01-95 by weight of the mixture.

The active compound can also be used in accordance with the well-known ultra-low-volume process with good success, i.e. by applying such compound if normally a liquid, or by applying a liquid composition containing the same, via very effective atomizing equipment in finely divided form, e.g. average particle diameter of from 50 microns, or even less, i.e. mist form, for example by airplane crop spraying techniques. Only up to at most about a few liters/ hectare are needed, and often amounts only up to about 1 quart/ acre, preferably 2-16 fluid ounces/acre, are sufiicient. In this process it is possible to use highly concentrated liquid compositions with said liquid carrier vehicles containing from about 20 to about 95% by weight, of the active compound, or even the 100% active substance alone, e.g. about 20-l0O% by Weight of the active compound.

Furthermore, the present invention contemplates methods of selectively killing, controlling or combating pests, i.e. fungi, nematodes and/or insects, which comprise applying to at least one of (a) such fungi, (b) such nematodes, (c) such insects, and (d) the corresponding habitat, i.e. the locus to be protected, a correspondingly pesticidally toxic amount, i.e. a fungicidally, nematocidally and/ or insecticidally effective amount, of the particular active compound of the invention alone or together with a carrier vehicle as noted above. The instant formulations or compositions are applied in the usual manner, for instance by spraying, atomizing, vaporizing, scattering, dusting, watering, sprinkling, pouring, and the like.

It will be realized, of course, that the concentration of the particular active compound utilized in admixture with the carrier vehicle will depend upon the intended application, and may be varied within a fairly wide range, depending upon the weather conditions, the purpose for which the active compound is used, and the type locus to be treated. Therefore, in special cases, it is possible to go above or below the aforementioned concentration ranges.

In commercial practice, the compositions when used as fungicides and nematocides according to the present invention are usually applied to the soil infected with fungi and nematodes.

The outstanding fungicidal, nematocidal and insecticidal activity of the particular active compounds of the present invention is illustrated, without limitation, by the following examples.

EXAMPLE 1.-FUNGICIDAL ACTIVITY Agar plate fungicide test [Mycelium growth] Solvent: 99 parts by weight distilled water.

Dispersing agent: Parts by weight polyoxyethylene sorbitane monolaurate (Tween 20).

To produce a suitable preparation of the particular active compound, 1 part by weight of such active compound is mixed with the stated amount of solvent containing the stated amount of dispersing agent.

The active compound preparation is added to potato dextrose agar (which has been liquefied by heating) in such an amount that the desired concentration of active compound is provided therein. After thorough shaking to achieve a uniform dispersion of the active compound, the agar is poured into Petri dishes under sterile conditions. Control dishes to which the active compound preparation has not been added are also set up.

When the mixture of substrate and active compound has solidified, the dishes are inoculated in the center of the plate with the species of fungi stated in the table and incubated at room temperature (2125 C.) for 7 days.

After this time, the extent of mycelial growth is determined in relation to the growth of the untreated control by measuring the average radius of the fungal colony from the central point of inoculation to the periphery of mycelial growth. The inhibition of fungal growth is expressed by the values to 10, wherein 0 means that there is no inhibition (full growth as in control) and 10 means that there is complete inhibition (absence of growth).

The particular active compounds tested, their concentrations in the agar used, the test fungi and the inhibition effects achieved can be seen from the following Table 1:

pylene oxide and propylene glycol (mol. wt. about 1000) (Pluronic L-6l) To produce a suitable preparation of the particular active compound, 1 part by Weight of such active compound is mixed intimately with 1 part by weight of the stated wettable powder base.

Separate 0.1 and 0.025 part by weight portions, respectively, of the resulting mixture are blended in turn with 2 parts by weight of clay (attapulgite) and 500 parts by weight of soil infected with the damping otf organism (Pythium), to provide 2 corresponding soil portions. The Pythium infested soil is prepared by mixing thoroughly Pythium cultures from 20-30 agar plates with 50 lbs. of steam-sterilized soil and adding 500 ml. of pea seeds to maintain virulence.

After standing at room temperature for 24 hours, each TABLE l.-AGAR PLATE FUNGICIDE TEST Coneen- Fu- Hel- Vertitration Cerato- Colletosarium Fuminto- Rhizcillium in cystis trichum lycoaarium sporium octom'a alb0 Pyth- Active compound p.p.m. ulmi obiculare persici nit/ale sativum solam' atrum ium (2 0 O 500 10 10 10 10 10 10 10 II I] 100 10 0 5 2 10 10 5 5 (C2H50)IPSSOHCICHC1I 10 8 0 2 0 5 10 2 5 II II 100 8 5 5 2 5 10 8 (C:H50)zP-SSCH:CC13 10 2 0 5 D 0 10 8 (41) O O 500 5 10 10 5 10 10 10 1 H 100 2 s 10 2 10 10 10 (CzHgOh -SSCCI=CHC1 10 0 5 5 0 8 8 8 (51)..." O O 500 8 B 10 10 10 10 H H 100 5 s 10 10 5 5 (C H 0)1P-S-S-CH=C Ch 10 0 0 5 5 0 0 (61) O O 500 10 10 10 l0 10 10 10 10 {L H 100 8 5 10 2 10 10 10 8 (CHaO)2 -S CHCl-CHC1 10 8 2 5 2 5 10 5 5 (71) O 500 8 8 l0 5 10 10 50 10 I] II 100 5 2 8 2 5 10 10 5 (CHsO)zPSSCH2-CC1: 10 2 0 0 0 5 0 0 0 (8 O O 500 10 1O 10 10 10 10 10 1] 100 10 10 10 10 10 10 10 (CH O)1PSS-CCl=CHCl 10 10 10 10 10 10 10 10 (9 O O 500 5 5 5 l0 10 10 II II 100 2 2 2 2 0 5 (CH30)zPS-SCH=CC12 10 0 0 2 2 0 2 (1O S O 500 l0 10 10 10 10 10 II [I 100 10 10 10 l0 10 10 (CzH5O)2PSSCHCl-CHC12 10 10 10 10 10 10 10 (11 O 500 5 2 10 5 10 5 II II 100 5 0 5 2 5 2 (CzH5O):PSSCH2CC13 10 0 0 5 l) 5 2 (12 O 500 8 5 5 2 8 10 H II 100 5 0 s o 5 s (C I-I O)1PSSCC1=CHC1 10 2 0 0 0 5 5 (13 S O 500 10 10 10 10 8 10 I II 100 8 8 10 10 5 10 (C2H O)z SS--OH=GC11 10 5 5 5 10 5 10 (141) S O 500 10 10 10 10 10 10 100 10 10 10 10 10 10 (CH3O)7PSSCHCI-CHC11 10 10 10 10 8 10 10 (15 O 500 8 8 10 10 10 10 II I! 100 5 2 l0 2 5 10 (CH3O)zPSS-CH2C C1: 10 2 0 5 0 0 10 (161)- S O 500 10 10 10 10 10 10 1 100 10 10 10 10 10 10 (CH 0)1PSS-CO1=CHC1 10 10 10 10 10 10 10 (1 S 0 500 10 10 10 10 10 10 I] H 100 10 10 10 8 10 10 (CH)2PS-S-CH:CO12 10 10 10 10 2 10 10 EXAMPLE 2.-FUNGICIDAL ACTIVITY Soil fungicide test [Rolled towel] Wettable powder base consisting of:

92 parts by weight hydrated silica (ultra fine, Hi-Sil 4 parts by weight sodium lignin sulfonate (Marasperse 4 parts by weight polycondensate of ethylene oxide, propound is mixed intimately with 1 part by weight of the stated Wettable powder base, and the resulting mixture is diluted with Water to the desired final concentration.

applied and the results obtained can be seen from the following Table 2:

TABLE 2.-SOIL FUNGICIDE TEST [ROLLED TOWEL] The active compound preparation is added to a vial 5 and then a standard nematode suspension (i.e., 1 drop of Active compound concen- Control tration in percent Active compound in p.p.m. of pythium (2:) 0 100 II II 0 (O;H5O):P-SSCHC1CHO12 (3a) O 100 0 II II 25 0 (C:H5O):P-SSCH1CC1;

(4g) O O 100 100 II II 25 100 (CaH O)aP-SS-C C1=CHO1 (5g) O 100 0 II II 25 0 (C:H5Q)zPSS-CH=CC11 (62)- O 0 100 80 II II 25 50 (OH;O):PSSCHCl-CHC11 (7:) 0 O 100 70 II II 25 (CH;O)2PSSCH2-C C1:

(8;) O 100 0 II II 25 0 (CH;O)PSS O C1=CHCl (92) 0 100 0 II II 25 0 (CH O)1PS-SCH=CCI2 (10,) S O 100 90 H II 25 70 (C;H O),PSSOHC1CHOI:

(11,) S O 100 70 II II 25 70 (C:H5O):PSSCHz-C Cl:

(12;) S O 100 0 II II 25 0 (OH;O);PS-S-C Cl=CHOl (13;) 0 100 70 II II 25 70 (C1H5O):P-SSCH=C Ch (14,) S O p 100 90 II II 25 80 (OH;O),PS-SCHC1CHC11 (151) 0 100 80 II II 25 so (CH;O)P-SSCH1CC1:

(162) O 100 100 H H 25 0 (CH30):PSSC C1=CHO1 (1 S O 100 100 ll ll 25 0 (GH O);PS S-CH=C Ola NOTE.10O p.p.m.=200 lbsJacre rate; 25 p.p.m.= lbs ./acre rate.

EXAMPLE 3.NEMATOCI DAL ACTION Saprophytic nematode test [Contact action] Wettable powder base consisting of:

92 parts by weight hydrated silica (ultra fine, Hi-Sil 233) 4 parts by weight sodium lignin sulfonate (Marasperse N) 4 parts by weight polycondensate of ethylene oxide, propylene oxide and propylene glycol (mol. wt. about 1000) (Pluronic L-61) To produce a suitable preparation of the particular 50-75 nematodes (Panagrellus and Rhabditi's) per drop of active compound preparation) is added thereto. The vial is incubated at room temperature (21-25 C.) for 48 hours. The ability of the particular active compound to immobilize saprophytic nematodes upon contact in aqueous suspension is determined microscopically by counting the number of non-motile (immobile) nematodes at the end of this time. The number of non-motile nematodes as compared to the total number of nematodes in the test vial determines the degree of effectiveness which is expressed as a percentage.

100% means that all, and 0% means that none, of the active compound, 1 part by weight of such active comnematodes have been immobilized.

mixed with the stated amount of the stated volatile solvent, and the resulting concentrate is diluted with further solvent to the desired final concentration.

TABLE 3.--SAPROPHYTIC NEMATODE TEST [CONTACT ACTION] Immobilization z)------------- I? H (CzH50)zPSS-CHC1-CHC12 (CzH O)zP-S-SCH=C C12 t)------------- I? I? (OHzO)zP-SS-CHCl-CHC12 (CH)lP-SSCH2C Cl:

(CH3O):PSSCH=C C12 (ID-nun...-

EXAMPLE 4.INSECTICIDAL ACTION One ml. of the resulting active compound preparation is placed in a dish and an additional 4 ml. of said solvent are added. The solvent is allowed to evaporate leaving a Confused flour beetle test [Contact action] uniform dry film residue. Ten confused flour beetles (T rzbolzum corzfusum) (Tribolium confusum) are then placed into the dish and covered with a muslin screen.

Solvent: 10 milliliters acetone.

To produce a suitable preparation of the particular After each of the periods of time stated in the followactive compound, 100 mg. of such active compound are ing table, the degree of destruction is determined and expressed as ap ercentage: 100% means that all, and

means that none, of the test creatures are killed.

The particular active compounds tested, the amounts used and the results obtained can be seen from the following Table 4:

One placed TABLE 4.CONFUSED FLOUR BEETLE TEST [CONTACT ACTION] Amount Flour beetle of active mortality in compound percent after applied exposure 0!- in mm. g./ Active compound dish 2 hrs. 18 hrs.

(2 O O 1, 000 100 100 {L H 100 100 100 (CsHsO): -SSCHC1CHC1: O 0

(34)"..- O 1, 000 100 100 II II 100 100 (C1H5O)QPSSCH1C Ch 10 0 (C;H O)SSCC1=CHC1 (O;H 0);P-S-SCH=C C11 (6 1, 000 100 100 H 100 30 (CHgO)zPS-SCHC1CHCh 10 0 0 (74) O O 1, 000 100 100 H H 100 (CH;O)=PS CH1C C1 10 0 0 (84)--." O O 1, 000 100 100 %.L H 100 100 100 (CHaO): SSCC1=CHC1 10 0 0 (9 O O 1, 000 100 100 II II 100 100 100 (CH3O)zP-SSCH=C Cl, 10 0 0 (10 S 0 1,000 100 100 I] II 100 0 0 (CH O)gP-SS-CHG1CHCh 10 0 0 11, s 0 1, 000 90 100 H II 100 0 0 (C1H50)1P-SSCH2CCI3 10 0 0 12. s o 1, 000 100 100 ll II 100 0 100 (C2H50): -SSC CI=CHC1 10 0 0 (134)--.- S O 1, 000 100 100 ll 1 100 0 30 (C1H 0)P-SSCH=CC11 10 0 0 (144) S O 1, 000 100 100 I 100 20 e0 (CH;O)=PS-SCHCl-CHC1 10 0 0 (154)..-. O 1, 000 100 100 100 o o (CH O)1PS-S-CH:CCl; 10 0 0 (164)--.. S 0 1,000 100 100 100 20 30 (CH;O)PSSCC1=CHC1 10 0 0 (1 S O 1, 000 60 100 l H 100 o 0 (CH0): --SSCH=CC1 10 0 0 N 0TE.1 mm. g.=0.000001 g.

EXAMPLE 5.-INSECTICIDAL ACTION I-Iousefly test [Contact action] (M usca domestica) Solvent: 10 milliliters acetone.

To produce a suitable preparation of the particular active compound, 100 mg. of such active compound are mixed with the stated amount of the stated volatile s01- 75 ing table, the degree of destruction is determined and to evaporate leaving a uniform dry film residue. Ten to flies (Musca domestica) are then placed in the jar and covered with a screen top. A cotton pad soaked in sugar-water solution is placed on top of the screen as food supply.

After each of the periods of time stated in the follow- 70 twenty TABLE 5.-HOUSEFLY TEST [CONTACT ACTION] Amount Mortality in perof active cent after excompound posure of houseapplied fly for in, mm. g./ Active compound dish 2 hrs. 18 hrs.

(24) O O 1, 000 100 100 100 20 100 (C2H5O)zPSSCHCl-CHC12 10 0 (34) O O l, 000 100 100 1] 100 50 100 (CzH O)zPSS-CH:CCI; 0 40 (44) (I) fl) 1,000 50 (CzH5O)1PS-SC Ol=CHCl (54) fil) (H) l, 000 50 (C:H50)2PSS-CH=C C12 (64) o o 1, 000 100 100 II II 100 0 100 (CH3O)2PSS-CHC1CHC12 10 0 50 (74) O 0 1,000 100 100 H H 100 0 so (CH O)zPS CH2C C1: 10 0 (84)- O O 1, 000 100 100 II II 100 90 100 (011:0):1 S- CCl=CHCl 10 60 100 (94) O O 1, 000 100 100 H I 100 90 100 (CHaO)qPS CH=CC1 10 70 100 (10 S O l, 000 90 100 II II 100 0 90 (C2H50)2PSSCHC1CHC1I 10 0 10 (114). S O 1, 000 70 100 H II 100 10 100 (C:H O)2PSSCH2CCl3 10 0 40 (12 S O 1, 000 90 100 [I 100 0 40 (C:H O)rPS-SC CI CHCI 10 60 (134).... O l, 000 90 100 II 100 0 so (C:H50)zP-SSCH=C C11 10 0 50 (14 O 1, 000 100 100 H H 100 0 4o (CH3O);PSSCHO1OHO1: l0 0 20 (154) S O 1, 000 100 100 ll ll 100 0 40 (CH30)2PSSCHr-CC1I 10 0 40 (164) S O 1, 000 100 100 II II 100 10 70 (CH3O):PSSCC1= 01101 10 0 30 (1 S O 1, 000 100 90 II II 100 0 60 (CH3O)nPSSCH=CCl2 10 O 40 NOTE.-1 mm. g.=0.000001 g. expressed as a percentage: 100% means that all, and 0% EXAMPLE 7 means that none, of the test creatures are killed.

The particular active compounds tested, the amounts used and the results obtained can be seen from the above Table 5:

The following further examples are set forth to illustrate, without limitation, the process for producing the active compounds according to the present invention:

EXAMPLE 6 o (CHaO) l S CHCl-CHClz (1r) 0,0-dimethyl-S-(1,2,2-dichlorovinyl sulfinyl) dithiophosphate 16.3 g. (0.1 mol) of 90% pure, 0,0-dimethyldithiophosphoric acid Were dissolved in 100 ml. of chloroform. 20 g. (0.09 mol) of 1,2,2-trichloroethyl sulfinyl chloride were added dropwise with stirring at 30-35 C. followed by refluxing of the reaction mixture until the evolution of hydrogen chloride had ceased (about 4 hours). Washing the resulting mixture with water until neutral, drying over MgSO filtering and then evaporating the filtered solution in high vacuum gave 29.5 g. (94% yield) of the desired 0,0-dimethyl-S-(1,2,2-trichloroethyl sulfinyl) dithiophosphate in the form of a yellow oil, 11 1.5654.

(CH 0) i -s- -C 01:01:01 (16.) 0,0-dimethyl-S- (1,2 dichlorovinyl sulfinyl) dithiophosphate 6.75 g. (0.02) mol) 0,0-dimethyl-S-(1,2,2-trichloroethyl sulfinyl (dithiophosphate were dissolved in ml. Skellysolve B and 2.02 g. (0.02 mol) triethylamine were added at 30 C. The hydrochloride which formed was fil- 17 tered after the reaction had reached completion. The Skellysolve B was stripped giving 5 g. (84% yield) of the stated compound in the form of a red-brown liquid, 11 1.5707.

Note: Skellysolve B is commercial hexane of boiling range 61-70 C. (143-158 F.).

EXAMPLE 9 (CzH50)z] s -CH=CCh (135) 0,0-diethyl-S- (2,2-dichlorovinyl sulfinyl) dithiophosphate 9.3 g. (0.05 mol) 0,0-diethyl dithiophosphate were dissolved in 100 ml. CHCl and 8 g. (0.05 mol) 2,2- dichlorovinyl sulfinyl chloride were added at 30 C., allowing HCl to escape. The reaction mixture was refluxed until no more HCl evolution could be detected, then washed with H O, dried over MgSO filtered and stripped, giving 15.2 g. (100% yield) of the stated compound in the form of a yellow liquid, n 1.5555.

EXAMPLE 10 (CgH50)g1 S- -CH=CC1g (55) 0,0-diethyl-S-(2,2-dichlorovinyl sulfinyl) thiolphosphate 6.9 g. (0.02 mol) 0,0-diethyl-S-(2,2,2-trichloroethyl sulfinyl) thiophosphate were dissolved in 100 ml. Skellysolve B and 2.02 g. (0.02 mol) triethylamine were added at 30 C. The reaction mixture turned dark as the amine salt was formed. After refluxing for three hours, the Skellysolve B was stripped, the residue dissolved in CHCl washed with H O, dried over MgSO filtered and stripped, giving 4.5 g. (72% yield) of the stated compound in the form of a red liquid, n 1.4914.

The following compounds are prepared in analogous manner:

(65) CHaO O Light yellow II oil 72% PS OHCICHCI2 yield 11 (85)--." CHaO O 0 Dark oil 67% II II yield 711) PS- CC1=CHGI 1.5026.

CHaO

(9 CHaO O 0 Orange oil 727 ll ll y d ma" 0 PSSCH=C C1: 1.5090.

(2 071150 0 0 Yellow oil 84% II II y l 7m P-S CHCICHC11 1.5100.

CrHsO (35)..-" 0211 0 0 0 Yellow 011 II 85% yield P S CHr-CCI: m) 1.5050

CQHSO (45)--- C2H O O 0 Dark oil II 78% yield PS-SCC1=CHC1 11D 1.5812.

CzHsO (155)-.-- CHQO S 0 Yellow oil II II 83% yield P S- CH:-CCI: 71D 1.5655.

CHaO

(1a). (31130 S 0 Dark 011 II II Yield PSSCH=CC1: m) 1.5520.

CHaO

(105).-.. CaHrO S 0 Yellow oil II II quant. yield P- S CHC1CHC12 my" 1.5576.

CZHBQ TABLEContinued (11 CzHsO S 0 Yellow oil H H 81% yield P-S-S-CHiCC1a "an" 1.5534.

CzHsO (12 0111 0 S 0 Dark oil H 7 y eld PSSCCI=CHO1 1m 1.5510.

CzHaO EXAMPLE 11 The corresponding 0,0-di- -n-propyl, -isopropyl, -nbutyl, -isobutyl, -sec.-butyl and -tert.-butyl -S-(2,2,2- and 1,2,2-trichloroethyland 2,2- and 1,2-dichlorovinylsulfinyl)-thiol and dithio phosphates may be prepared in analogous manner from the appropriate starting thiol and dithio phosphoric acid esters (II) and sulfinyl chlorides (H1) or (IV), as the case may be, such final compounds similarly possessing relatively strong fungicidal, nematocidal and insecticidal properties.

As examples of sulfinyl thioland dithio-phosphates of Formula I in which R is ethyl or vinyl having three or two chloro substituents, respectively, and X is oxygen or sulfur and R is lower alkyl of 1-4 carbon atoms according to the present invention, there may be mentioned in particular:

0,0-dimethyl-S- 1,2,2-trichloroethyl sulfinyl -thiolphosphate,

O,'O-dimethyl-S- 2,2,2-trichloroethyl sulfinyl -thiolphosphate,

0,0diethyl-S-(1,2,2-trichloroethyl sulfinyl -thiolphosphate,

0,0-diethyl-S- 2,2,2-trichloroethyl sulfinyl -thiolphosphate,

0,0-dirnethyl-'S- 1,2,2-trichloroethyl sulfinyl) -dithiophosphate,

0,0-dimethyl-S-(2,2,2-trichloroethyl sulfinyl)-dithiophosphate,

O,-O-diethyl-S-(1,2,2-trichloroethyl sulfinyl)-dithiophosp ate,

0,0-diethyl-S-(2,2,2-trichloroethyl sulfinyl)-dithiophosphate,

0,0-di-n-propyl-S-(1,2,2-trichloroethyl sulfinyl)-thiolphosphate,

0,0-diisopropyl-S-( 1,2,2-trichl0roethyl sulfinyl -thiolphosphate,

0,0-diisopropyl-'S- (2,2,2-trichloroethyl sulfinyl)-thiolphosphate,

0,0-diisopropyl-S-(2,2,2-trichloroethyl sulfinyl)-dithiophosphate,

0,0-diisopropyl-S- 1,2,2-trichloroethyl sulfinyl) -dithiophosphate,

0,0-di-n-butyl-S-(2,2,2-trichloroethyl sulfinyl)-thiolphosphate,

0,0-di-n-butyl-S- (2,2,2-trichloroethyl sulfinyl -dithiophosphate,

0,0-di-n-butyl-S- 1,2,2-trichloroethyl sulfinyl -dithiophosphate,

O, O-dimethyl-S-( 1,2-dichlorovinyl sulfinyl -thiolphosphate,

0,0-dimethyl-S- (2,2-dichlorovinyl sulfinyl -thiolphosphate,

0,0-diethyl-S- 1 ,2-dichlorovinyl sulfinyl) -thiolphosphate,

0,0-diethy1-S(2,2-dichlorovinyl sulfinyl)-thiolphosphate,

0,0};dimethyl-S- 1,2-dichlorovinyl sulfinyl) -dithiophosp ate,

0,0-dimethyl-S-(2,2-dichlorovinyl sulfinyl)-dithiophosphate,

0,0-diethyl-S-(2,2-dichlorovinyl sulfinyl)-dithiophosphate,

0,0l;diethyl-S-(1,2-dichlorovinyl sulfinyl)-dithiophosp ate,

0,0-di-n-propyl-S- (2,2-dichlorovinyl sulfinyl)-dithiophosphate,

0,0-diisopropyl-S-( 1,2-dichlorovinyl sulfinyl -thiolphosphate,

0,0-diisopropyl-S-(2,2-dichlorovinyl sulfinyl)-dithiophosphate,

0,0-di-n-butyl-S- (2,2-dichlorovinyl sulfinyl) -dithiophosphate,

0,0-di-n-butyl-S- 1,2-dichlorovinyl sulfinyl) -dithiphosphate,

0,0-di-sec.-butyl-S-(1,2-dichlorovinyl sulfinyl)-thiolphosphate,

0,0-di-sec.-butyl-S- (2,2-dichlorovinyl sulfinyl -dithio phosphate, and the like.

It will be realized by the artisan that all of the foregoing compounds contemplated by the present invention possess the desired strong pesticidal, especially insecticidal, nematocidal and fungicidal, properties for combating insects, nematodes and fungi, with regard to a broad spectrum of activity, as well as a comparatively low toxicity toward warm-blooded creatures, and a concomitantly low phytotoxicity, enabling such compounds to be used with correspondingly favorable compatibility with warm-blooded creatures and higher plants for more effective control and/ or elimination of insects, nematodes and fungi by application of such compounds to such insects, nematodes and fungi and/or their corresponding habitat.

It will be appreciated that the instant specification and examples are set forth by way of illustration and not limitation, and that various modifications and changes may be made Without departing from the spirit and scope of the present invention.

What is claimed is:

1. Method of combatting a pest selected from the group consisting of fungi, nematodes and insects which comprises applying to such fungi, nematodes, insects or their habitat, an effective amount of a compound of the formula noni -s-sqt' in which R is lower alkyl of 1-4 carbon atoms,

R is selected from the group consisting of trichloroethyl and dichlorovinyl, and

X is selected from the group consisting of oxygen and sulfur.

2. Method according to claim 1 wherein R is C alkyl, R is selected from the group consisting of 1,2,2- trichloroethyl, 2,2,2-trichloroethyl, 1,2-dichlorovinyl and 2,2-dichlorovinyl, and X is selected from the group consisting of oxygen and sulfur.

3. Method according to claim 1 wherein such compound is 0,0 dimethyl-S(2,2-dichlorovinyl-sulfinyl)-thiolphosphate of the formula 4. Method according to claim 1 wherein such compound is 0,0 dimethyl-S-(1,2,2-trichloroethyl-sulfinyl)-dithiophosphate of the formula I! H (CH OhP-S-S-CHOl-C c1,

5. Method according to claim 1 wherein such compound is 0,0 dimethyl-S-( l,2-dichlorovinyl-sulfinyl)-thiolphosphate of the formula 20 6. Method according to claim 1 wherein such compound is 0,0 diethyl S (l,2,2-trichloroethyl-sulfinyl)-dithiophosphate of the formula 0 (CzH5O)21 -SL lCHClOHC1q 7. Method according to claim 1 wherein such compound is 0,0 diethyl-S-(2,2,2-trichloroethyl-sulfinyl)-thio1phosphate of the formula 8. Method according to claim 1 wherein such compound is 0,0 diethyl-S-(1,2-dichlorovinyl-sulfinyl)-thiol-phosphate of the formula 9. Method according to claim 1 wherein such compound is 0,0 diethyl S (2,2,Z-trichloroethyl-sulfinyl)-dithiophosphate of the formula 10. Method according to claim 1 wherein such compound is 0,0 dimethyl-S-(1,2-dichlorovinyl-sulfinyl)-dithiophosphate of the formula Hs0)zI S & CC1=OHCl 11. A composition for combatting fungi, nematodes and insects containing an effective amount of a compound of the formula X (R0)zi S- SR' in which R is lower alkyl of l-4 carbon atoms, R is selected from the group consisting of trichloroethyl and dichlorovinyl, and X is selected from the group consisting of oxygen and sulfur, in admixture with a member selected from the group consisting of a solid diluent, a solid carrier, a liquid diluent and a liquid carrier containing a surface active agent.

12. A composition according to claim 11 wherein said compound is 0,0-dimethyl-S-(2,2-dichlorovinyl-sulfinyl)-thiolphosphate, 0,0-dimethyl-S-1,2,Z-trichloroethyl-sulfinyl)- dithiophosphate, 0,0-dimethyl-S- 1,Z-dichlorovinyl-sulfinyl) -thio1- phosphate, 0,0-diethyl-S-( 1,2,Z-trichloroethyl-sulfinyl dithiophosphate, 0,0-diethyl-S-(2,2,Z-trichloroethyl-sulfinyl)- thiolphosphate, 0,0-diethyl-S-( 1,Z-dichlorovinyl-sulfinyl) -thiolphosphate, 0,0-diethyl-S-(2,2,2-trichloroethyl-sulfinyl)- dithiophosphate, or 0,0-dimethyl-S-( 1,Z-dichlorovinyl-sulfinyl) -dithiophosphate.

References Cited FOREIGN PATENTS 941,810 1'1/1963 Great Britain 260-934 ALBERT T. MEYERS, Primary Examiner N. A. DREZIN, Assistant Examiner 

